Method of making aqueous dispersions containing polyvinyl acetate and wax



Patented July 23, 1946 I UNITED STATES PATENT OFF 2,404,519 ICE METHOD OF MAKING AQUEOUS DISPER- SION S CONTAINING POLYVINYL ACETATE AND WAX George Osman Morrison and Henry Michael Collins, Shawinigan Falls, Quebec, Canada, assignors to Shawinigan Chemicals Limited, Montreal, Quebec, Canada, a corporation of Canada No Drawing. Application May 15, 1943, Serial No.

487,186. In Canada November 4, 1942 INTRODUCTION OBJECTS It is a principal object of the present invention to provide new compositions of matter including polyvinyl acetate emulsions which are suitable for use in the preparation of waterproof sheets or films, or useful for forming waterproof coatings on various materials. It is a further object of the invention to provide a composition embodying, in emulsion form, polyvinyl acetate as a filmforming constituent, and a moisture-proofing agent with or without other modifying constituents such as for instance, softeners and plasticizers. Further objects are to provide improved methods of making these compositions, improved methods of moisture-proof coating, improved coatings and improved coated articles.

Tm: INVENTION These objects and others are accomplished according to the invention by a composition which includes an aqueous emulsion of polyvinyl acetate as a principal film-forming constituent, an oleag inous or waxy protective agent, the composition being capable of forming a film having moisture-proof characteristics. This film may be laid down by ordinary methods of coating, but preferred results are achieved by flashing the film,

that is, by subjecting it to a blast of hot air at a temperature above the melting point of the waxy agent. This causes the formation of .a bloom which protects the film from re-emulsification or from otherwise disintegrating.

Articles made from materials which are not resistant to water and coated in this manner may 3 Claims. (Cl. 260-28) Example I I This example demonstrates a preferred method of manufacturing a polyvinyl acetate emulsion according to the invention.

be rendered completely moisture-proof. This is particularly advantageous in the case of containers for aqueous materials.

EXAMPLES To illustrate the invention in more detail, several examples will be given of specific embodiments. These data are intended in an illustrative and not in a restricting sense.

' Vinyl aceta In one procedure th following constituents were employed at the approximate concentration set out:

1 By weight of the total charge.

An aqueous solution of the emulsifier was charged into a kettle equipped with a reflux condenser and stirring blades. One type of equipment, as used according to the following conditions, includes an aluminum pot about 8 inches high by about 6 inches outside diameter having aconcave bottom and no baffles. The stirrer shaft is of stainless steel. It embodies half an inch from the bottom 4 blades in a cluster 1 inch by inch bent at 45 for downward thrust; four inches from the bottom, a pair of blades (one at each side of the shaft) each 2 /2 inches by inch bent at an angle of 45 for downward thrust. The useful speeds, of the blades areabout 500 to about 1800 revolutions per minute.

Stirring was started. The catalyst and water were added. Two minutes, stirring at about 1200. revolutions per minute was allowed and then the monomeric vinyl acetate was added slowly. The

whole charge was then agitated for about 5 minutes in the cold to complete emulsification of the monomer. Stirring was continued at about the same speed and the temperature of the jacket raised to about 70 C. and maintained at this temperature until the temperature of the charge reached about 66 C.

Then, as the reaction gathered momentum and reflux commenced, the temperature of the jacket was gradually and suitably reduced in order to maintain a moderate reflux of about 1 percent to about 1 percent of the total charge per hour. Finally, the jacket temperature was reducedin order to regulate the reflux at the low rate. When the temperature of the charge had reached about 70 C. the temperature of the jacket was graduallyraised from its minimum to about 82 C.

- Thus, as the temperature of the charge increased,

charge followed closely behind that of the jacket. When they were equal at about 82 C. reflux ceased and polymerization of the monomer was substantially complete.

The wax was then added and the emulsion stirred for about minutes with the temperature maintained at about 82 C. The charge was then cooled down to about 25 C. This was done over a period of about one hour with stirring continued. The agitator was then stopp d and the batch of finished emulsion discharged. The resulting composition had substantially the following characteristics:

Viscosity of emulsion at 20 C centipoises 300 two fine cardboard containers C and D substantially as in Example 2, at a temperature of about.

about 90 C. Where there was no plasticizer present in the polyvinyl acetate, the resultant film was brittle. The composite film was made up of about mil polyvinyl acetate and about mil wax. v

The container was filled with water which was kept at about 30 C. After about two weeks the container and film were intact, but creasing of the cardboard resulted in extensive leakage. There was no re-emulsification.

v 1 fiiiitfi tiaiaaaa;; 11:':: 1';1iitiif:: 33 The film 2 container wasallowed to dry Polyvinyl acetate viscosity centipoises 30 at about C. Re-en ulsification of the film- Stability Good began after about 1 hour 5 contact with the water and the container collapsed after about 10 hours 0 1 t ta charge l 20 contact with the water.

Emmple 2 te the respective char- Example 4 act'Illiq ztegsngfile 1313:22 1??? ind flashed films thAn emulsion was prepared as in Example 1 with I e exception that the waxy agent was increased lald dOWn o a composltlon made according to to about 60% of the polyvinyl acetate Example 1. 5

A mm was as from this by sash" asin stiieitiitl tfiffilitifif titf gs g g igg g ig g g i gg figgzi gg and the containers were subjected to the same tests as in Examples 1 and 2 to determine their made from fine 9 of t usually ability to withstand water. The results were emptoyed for making hqmd c9ntamers' film 3 similar to those obtained with the flashed films cgatmgothe surface of container A was dried at of Examples 1 and 2 with the exception that the a out C.

The film was about 1 mil in thickness. It was films of this example were more elastic. pliable-and elastic. Water at about C. was Emmple 5 ,poured into this container. After about 72 hours The procedure of Example 1 was repeated with at room temperature t e c t i Was p hydrogenated cotton seed oil replacing about 25% cally soaked through and had collapsed. The of the paraflin wax, the oil serving as u film had most o p e y re-emulslfiedcizer for the wax. From the resulting emulsion The coating on container B was dried at about a film was formed on t rface of the 20 C. It was then fiashe for abqut three 40 tamer. The film was flashed and cooled and minutes in an air oven with a blast o heated tests for moisture-proof characteristics were carto about 110 C. The film was about 1 mil in ried out substantially as in Example 2. The film thickness. t wa Dhable nd e a A bloom had the same excellent moisture-proof characterof wax had formed on the surface. Wa r at istics as container B (Ex. 1) and was at the same about 30 C. was poured into this container. ti more pliable and more capable f being After about two weeks at room temperature the creased t t injury t t fi1m film on the container was still intact. No re- Ea: m l 6 15 emulsificati'on of the film could be detected. Cones tain'ers coated similarly to B were acceptable to In 1 to demonstrate the manufacture a d the trade for containing aqueous materials. use Q dlfierent films formed according to the n- Exambze 3 vention, the following Examples 6 to 15 are given. According to the natures and approxi- The following example demonstrates the charmate concentrations of the constituents set out acteristics of a film prepared from a polyvinyl in the table, emulsion were made substantially acetate emulsion containing no wax but subsein accordance with Example 1. Containers were quently coated with wax. coated with these emulsions and tested for per- An emulsion was prepared substantially as in formance substantially as in Example 2, and the Example 1 with the exception that no wax was performance of the coatings was as indicated in incorporated. A film was cast on the inside of the table.

Table I Approximate Ex. Plasticizer Wax plasticizer Pliability afiggfgg of 128E336;

bility offilm Per cent Nil 30 Petroleum jelly, 15% Petroleum jelly, 20%.. 70 Petroleum oil, 12%...-

mgtssssntsts; as-an;- i$

Petroleumjelly, 15% "do 100 Nil Very pliable.-. 100 do "do 100 The coating of Example 6 was not flashed, whereas those of Examples 7 to 15 were flashed.

1 Example 16 The emulsion was made as in Example 1 with the exception that the wax was added to the charge'before the start of the reaction.

The emulsion was used for coating containers in procedures similar to those of Example 2. The results as regards the characteristics of the films and their moisture-proof performance were substantially the same as those of Example 2.

DETAILED DESCRIPTION While the examples demonstrate various specific types of coating-emulsions according tov the invention, it will be obvious to one skilled in the art that the particular constituents, compositions, conditions and concentrations set out may be varied widely within the scope of the invention.

Pao'rnc'rrvr: AGENT For instance, the nature of the protective agent may be varied. Suitable agents are oleaginous or waxy materials such as for instance; hydrogenated natural oils and fats, for example, cotton seed oil, linseed oil; saturated natural oils, for instance, animal oils, sperm oils; paraffin type oils and waxes, for example, micro-crystalline paraffin wax and parafiin oil; or mixtures of these substances. These agents or mixtures thereof should have a melting point of between about 47 F. and about 140 F. and the necessary flexibility when solid and other coating characteristics as will be understood by those skilled in the art. The melting point will vary depending upon the particular use to which the coating is put. It is preferable that the melting point be between about 100 F. and about 140 F. Preferred agents are paraffin waxes.

The useful range of concentration of the protective agent is between about 12% and about 40% calculated by weight on the total charge.

The preferred range of concentration is between about 12% and about 20% Monrmrmc AGEn'rs The coating emulsion is preferably modified to make the resulting film more flexible and to render it more flowable than it would be with wax alone as a protective agent. This may be effected by adding a softener for the wax and/ora plasticizer for the resin. An effective softener is hydrogenated cotton seed oil, conveniently the commercial product known as Crisco, employed at concentrations of between about 3% and about 15% of lthe total charge. Other oleaginous softteners such as for instance petroleum jelly, mayticizers are preferably used at concentrations of between about 3% and about 5% by weightofj the total charge. When the coating is fla'shed according ,to the present invention: the wax bloom has the effect of isolating the contents Suitable plasticizers of the container from the plasticizer. Thus the concentration of the plasticizer may be increased over what might otherwise be thought possible without danger of contaminating the contents.

MANUFACTURING PROCEDURE While substantially conventional methods are employed in making the emulsion, in order to improve still further the qualities of the emulsion as a coating material, special steps are taken in the process of manufacture. Up to the completion of polymerization the procedure is conventional for the manufacture of polyvinyl acetate emulsions, with the exception that the waxy agent is added as an additional phase either prior to, during, or after polymerization. The procedure then departs from the conventional in that the wax-containing emulsion is cooled very slowly, i. e. over a period of about 40 minutes to about 2 hours or more, from the upper temperature resulting from polymerization of about 84 C. to room temperature of about 20 C. By following this procedure, emulsions can be made having viscosities of between about 200 and about 2000 centipoises. Those in the neighborhood of 300 centipoises are preferred. These emulsions fiow readily, thus havin excellent characteristics for coating. In contrast, similar emulsions which were cooled rapidly, exhibited viscosities of as high as 7,000 centipoises. The latter emulsions were not stable and films laid down from them were poorly flexible. From this, it would appear that slow cooling causes the formation of small discrete wax particles as a third phase of the emulsion. In most cases, these wax particles were of a size between about 4p and about 2011..

In general, the normal constituents of the emulsions, e. g. emulsifying agents, catalysts, modifying agents, etc. may be those generally employable in the manufacture of aqueous emulsions of polyvinyl acetate. Preferred types of emulsions may, however, be manufactured by followin the teachings of the present application in conjunction with those of the following copending applications, H. M. Collins, S. N. 457,337, Sept. 4, 1942, relating to the use of emulsifying agents of particular types, and M. Kiar, S. N.

457,339,Sept. 4, 1942, relating to the use of particular conditions to influence the characteristics of the resulting polyme Y COATING The formation of the film or coating on the surface of the article being coated may be effected in a conventional manner. In order, however, to achieve the preferred results of which the present invention is capable using a relatively thin coating, the dried coating is flashed at a temperature above the melting point of the waxy protective agent. This apparently has the eifect of bringing the wax to the surface to form a bloom which acts to prevent penetration by moisture.

The thickness of the films formed may vary considerably. Satisfactory moisture-proof films for commercial purposes are in the neighborhood of 1 mil in thickness.

Thefilms may also be modified by treatment with the pigments or fillers usually employed with polyvinyl acetate resins. Food products and other articles can be coated directly with films as opposed to coating a-container. Self-sustaining ,fi l s can also be formed and rendered waterproof by the present teachings.

anemia V O Y, 7

These coatings have a widevariety or uses.

Many other In this specification, the term "waterproof coating is intended to indicate a coatin able jto withstand water effectively for the purposes to which the coated material is to be put. For instance, containers for aqueous liquids must'be sufliciently water-proof that the container will, under the conditions of manufacture, handling and use, stand up to the satisfaction of the trade 1 and of consumers.

It will be understood that, without departing from 'the-spirit'of the invention or the scope of fthe claims, various modifications may be made in the specific expedients described. Thelatter are illustrative only and not offered in a restricting sense, it being desired that only 'such limitations shall be placed th'ereon as may be required by the state of the prior art. y

We claim: V a

l. A process of preparing a coating composition comprising adding a wax to an aqueous dispersion of polyvinyl acetate produced by emulsion polymerization. in the presence of an emulsifying agent effective to stabilize said dispersion, said polyvinyl acetate beingpresent in an amount ranging from about 30 to about 70% of the said dispersion, said 'wax being present in an amount rangingfroxn about 12 to about 40% of the total composition, the wax being added when the dispersion has a temperature above the melting point of the wax, then cooling the dispersion slowly with stirring to about room temperature during a period of about 40 minutes to 2 hours whereby the ,wax constitutes a ph'ase of said dispersion in small discrete particles.

2. A process accordingto claim 1 wherein the V wax is a parafiin wax having a melting point within a range from about 47 F. to about 14=0f F. 3. A process according to claim 1 wherein there 'is added to the dispersion an oleaginous softener for the wax and a plasticizer for-the polyvinyl acetate.

GEORGE OSMAN MORRISON. HENRY MICHAEL COLLINS. 

